Performance boosting UV-absorbing compounds

ABSTRACT

UV-absorbing compounds are disclosed that are derived from at least: (a) a UV absorber having at least one hydroxyl group, primary amine group, or secondary amine group, (b) a coupling agent having anhydride functionality, and (c) a graft host comprising an unsaturated fatty acid. These compounds absorb, scatter, deflect, or scatter ultraviolet radiation in a variety of personal care and performance chemical applications. 
                         
R″ and R′″ are alkyl or alkenyl groups that naturally occur in oil.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of U.S. patent application Ser. No.12/688,980, filed Jan. 18, 2010, which is claims benefit of U.S.Provisional Application Ser. No. 61/145,268, filed Jan. 16, 2009. Theentire contents of the related applications set forth are herebyincorporated by reference.

FIELD OF THE INVENTION

The disclosed invention relates to compositions that boost theperformance of ultraviolet (UV) absorbers, comprising (a) a UV absorberhaving at least one hydroxyl group, primary amine group, or secondaryamine group, (b) a coupling agent having anhydride functionality, and(c) a graft host comprising an unsaturated fatty acid. Suchperformance-boosting compositions enable novel formulations forabsorbing, reflecting, and/or scattering radiation.

In preferred embodiments, the UV absorber exhibits UV-A activity, UV-Bactivity, or both UV-A and UV-B activity, the coupling agent is maleicanhydride, and the graft host is an unsaturated oil or unsaturated fat.The compositions may be employed in personal care and industrialapplications.

DESCRIPTION OF RELATED ART

It is now generally accepted that ultraviolet (UV) radiation can be aserious health hazard. Even a limited exposure to solar radiation cancause short- and long-term skin damage, such as erythema, burns,wrinkles, lentigo (“liver spots”), skin cancers, keratotic lesions, andother cellular changes. There is a greater risk for developing suchconditions for those who send prolonged time in the sun, such as fortheir occupation or during recreation.

UV radiation is just one portion of the electromagnetic spectrum withwavelengths from about 100 nm and about 400 nm, and is further dividedinto three subregions. UV-A radiation, from about 320 nm to about 400nm, has the longest wavelength within the UV spectrum, and consequentlyis the least energetic. While UV-A rays can induce skin tanning, theyare liable to induce adverse changes as well, especially in the case ofsensitive skin or of skin which is continually exposed to solarradiation. In particular UV-A rays cause a loss of skin elasticity andthe appearance of wrinkles, leading to premature skin aging. UV-B rayshave shorter wavelengths, from about 290 nm to about 320 nm, and theirhigher energy can cause erythema and skin burns which may be harmful.The third subgroup, UV-C has the shortest wavelengths, from about 200 nmto about 290 nm, and the highest energy. The Earth's ozone layereffectively filters much UV-C radiation from reaching the ground.Nonetheless, UV-C rays can be generated from tanning bed devices.

In addition to harming the skin, UV radiation can injure the hair,resulting in color changes (especially for color-treated hair),embrittlement, and a loss in aesthetics (e.g., shine, manageability).

UV radiation damage is not limited to the skin and hair, as inanimateobjects exposed to solar radiation can experience changes related tocolor, hardness, and structural integrity, which can contribute toaesthetical and functional deterioration. Thus, there is the very realand demanding need for compositions that protect the skin, hair, andobjects from UV rays, especially UV-A and UV-B radiation. Of specialinterest are compositions that provide broad UV-spectrum protection fromboth UV-A and UV-B radiation.

Broadly speaking, para-aminobenzoic acid (PABA) exhibits a common traitshared with many UV absorbers/filters. The molecule possesses bothelectron withdrawing and electron accepting groups, providing resonancedelocalization that coincides with the absorbed energy of UV radiation:

However, PABA is a highly polar molecule, making it water soluble, andgiving it low persistence, meaning that it is not highly retained on theskin after swimming or perspiring. In addition, due to extensiveintermolecular bonding, PABA exists as a solid, which may furthercomplicate its formulation. Thus, there exists the need to improve thepersistence of UV absorbers, especially those that are water-soluble,and to provide formulation flexibility.

UV absorbers may exhibit photolability, in which the absorbed energycauses photodegradation and/or photoreactivity, and thus reduce itsefficacy. Such photolability may result from irreversible isomerisms(i.e., keto-enol tautomerism and cis-trans isomerism), photocleavage,and/or photoaddition, and may be formulation sensitive, (e.g., blends ofavobenzone and octinoxate). Examples of photolabile UV absorber include,without limitation: avobenzone, PABA derivatives, cinnamates, anddibenzoyl methane derivatives, all of which degrades over time, andreduce UV protection. Hence, there exists a need to stabilize UVabsorbers from photodegradative effects.

Additionally, there exists the need to enhance the efficacy of UVabsorbers without increasing their content in the formula, since amaximum addition level frequently is regulated. This efficacy need isespecially important for avobenzone, a highly effective UV-A absorber.Avobenzone is subject to keto-enol isomerization due to formulationdependencies (e.g., solvent, other UV absorbers):

The enol tautomer (left) has its maximum absorbance at 357 nm, whichidentifies it as a UV-A absorber. Unfortunately, avobenzone is subjectto bimolecular reactions (viz, via cleavage mechanisms) that alter themolecule's structure and decrease its effectiveness as an UV absorber.Hence, an effective method is needed for stabilizing labile chromophoreslike avobenzone in order to enhance their efficacy without increasingtheir addition level.

Methods for stabilizing chromophores, and in particular UV absorbers,are known in the prior art. For example, in U.S. Pat. No. 4,868,246teaches polymer chemistries having UV absorbers bonded to recurringunits:

in the polymer backbone, on grafted side chains, as pendant units, or ascombinations thereof. The group N-G is the residue of a primary amino orhydrazido substituted stabilizer group selected from (a)2-hydroxybenzophenones, (b) 2-(2-hydroxyphenyl)-2H-benzotriazoles, (c)aryl salicylates, or (d) oxalic acid amides. A number of potentialmaleic anhydride polymers are potential stabilizers for the UVabsorbers, and include: (a) styrene-maleic anhydride, (b) alternatingcopolymers of maleic anhydride and alpha-olefins, (c) alkyl vinyl ethersand maleic anhydride, (d) maleic anhydride modified polyolefins, (e)maleic anhydride adducts of hydrogenated polymers or copolymers, and (f)maleic anhydride adducts of EPDM. The '246 patent exclusively teachespolymeric compositions, and does not contain reference to UV absorberbound to a graft host via an anhydride coupling agent.

A similar approach is taught in U.S. Pat. No. 4,857,596 for thermallystabilizing antioxidants.

Two radiation-absorbing polymer chemistries are taught in U.S. Pat. No.6,255,405. The '405 patent is directed toward radiation-absorbingcompositions and coatings, particular for “forming a bottomanti-reflective coating upon producing an integrated circuit.” Thepolymeric compositions comprise two recurring units, the first havingthe formula:

wherein R_(a) and R_(b) may be the same or different and representhydrogen, an alkyl group or other organic groups, Ar represents anorganic chromophore, and n represents 0 or an integer of 1 or more; andthe second recurring unit having the formula:

wherein R_(c) and R_(d) may be the same or different and each representshydrogen, an alkyl group, a carboxyl group, or other organic groups, andZ represents hydrogen, a substituted or non-substituted alkoxyl group, asubstituted or non-substituted alkyl group, a halogen atom, —CN, analkylcarbonyloxy group, an imide group, a substituted or non-substitutedcarbamoyl group, a substituted or non-substituted oxycarbonyl group, ora substituted or non-substituted phenyl group.

The '405 patent recognizes the use of its UV absorber compounds only forelectrical circuit board applications.

U.S. Pat. No. 6,492,455 discloses compositions comprising the reactionproduct of a C₆+ alpha olefin/maleic anhydride copolymer with apolyfunctionalized secondary or tertiary amine. The resulting copolymeris an alternating copolymer of an olefinic monomer and a maleicanhydride with a polyfunctionalized secondary or tertiary amine. Usesincludes hair spray and water-proof sunscreen compositions.

U.S. Pat. No. 7,361,710 describes compositions comprising the reactionof (a) an unsaturated vegetable oil and an enophile or dienophile havingacid, ester, or anhydride functionality and (b) a functional vinylmonomer. For example, soybean oil is reacted with maleic anhydride, toyield a maleated vegetable oil:

The maleated oil is reacted with hydroxyethyl methacrylate,2-(tert-butylamino)ethyl methacrylate, or glycidyl methacrylate.

Another maleated oil is described in U.S. Pat. No. 3,428,589, which isdirected to polycarboxylic acid anhydride resins of high viscosity, andfor such resins of voltage capabilities. This invention discloses theheating (1) of a dry oil, a modified drying oil, or a mixture thereof,and (2) and alpha, beta-ethylenically unsaturated dicarboxylic acidanhydride, which is heated until a polycarboxylic acid anhydride resinproduct (i.e., an adduct) with a desirably high viscosity is obtained.The polycarboxylic acid anhydride resin is then reacted with an organicaromatic primary or secondary amine, as represented in the followingreaction:

wherein R′ represented the drying oil portion of the adduct, and R″ ishydrogen or alkyl. The '589 patent specifies that the organic aromaticprimary or secondary amine has from 1 to 20 carbon atoms, preferablyfrom 1 to 10 carbon atoms. The '589 patent discloses compositions forelectrocoating baths, compositions with high throwing power, and ofexcellent intermediate voltage capacity.

Additional disclosure related to anhydride-functionalized vegetable oilsis provided by Aydin, S., et al., Prog Org Coat, 51, 273-279, 2004; andby Guner, F. S., et al., Prog Polym Sci, 31, 633-670, 2006, both ofwhich are incorporated in their entirety by reference. While these worksdescribe methods to graft anhydride functional groups onto vegetableoils, they do not teach subsequent grafting of UV absorbers onto theanhydride moiety.

Functionalized poly(alpha olefin-maleic anhydride) polymers are thesubject of application PCT/EP2007/051697. This functionalized copolymerhas the structure:

wherein X is —O— or —NH—, and —X—R₂— is a functional radical selectedfrom a group that includes natural molecules that are UV absorbers, suchas tannins, flavonoids, thymol, caffeic acid esters, and vitamin E.

Despite advances in designing UV absorbers and in developing formulationblends, there remains a commercial demand for UV absorber compositionswith boosted performance, especially for single compositions thatprovide full UV-spectrum protection, enhance water-resistance, reducetendency for skin penetration, and stability especially for labile UVabsorbers. The compositions disclosed herein uniquely accomplish theseproperties.

SUMMARY OF THE INVENTION

It has been discovered that performance-boosting UV absorber compoundscan be derived from at least (a) one UV absorber having at least onehydroxyl group, primary amine group, or secondary amine group, (b) acoupling agent having anhydride functionality, and (c) a graft hostcomprising an unsaturated fatty acid. Such compositions can be producedvia three routes, the preferred being that at least one UV absorber isreacted with the preformed ene grafting reaction product between amolecule having anhydride functionality and a graft host comprising anunsaturated fatty acid. The UV absorber compounds can be produced withor without added reaction solvent, initiator, or catalyst, or blendsthereof.

In preferred embodiments, the coupling agent is maleic anhydride.

In other preferred embodiments, the graft host comprising an unsaturatedfatty acid is an unsaturated fatty acid, an unsaturated liquid oil, oran unsaturated solid fat.

In especially preferred embodiments, the ene grafting reaction productis an unsaturated maleated vegetable oil.

In another embodiment of the invention, the chromophore is a UVabsorber, and in preferred embodiments, the chromophore comprises a UV-Aabsorber or a UV-B absorption activity. In especially preferredembodiments, the UV absorber comprises at least one UV-A active and atleast one UV-B active, being provided by one or more UV absorbers.

These UV absorber compounds exhibit better resistance (permanence), andoffer customizable UV spectrum protection. A result of formulationflexibility in selecting the fatty acid, the skin penetration of the UVabsorbers may be reduced or essentially eliminated. Remarkably, singlemolecular entities are produced that offer both UV-A and UV-Bprotection, providing enhanced UV protection while simultaneouslyreducing formulary burden. Even more surprisingly, labile UV absorbers,such as avobenzone, may be stabilized when blended with these UVabsorber compounds, thus further increasing their use as well.

In a preferred embodiment, the chromophore compositions are used inpersonal care applications. In especially preferred embodiments, the UVabsorber compounds are used in sun-care formulations.

In other preferred embodiments, the performance-boosting UV absorbercompounds are used in non-personal care applications, such as adhesives,coatings, construction materials, encapsulations, ink, printing,plastics, and packaging applications.

DETAILED DESCRIPTION OF THE INVENTION

The terms “ultraviolet” and “UV” are taken to mean electromagneticradiation, especially solar electromagnetic radiation, with a wavelengthfrom about 100 nm to about 400 nm, and includes the UV-A, UV-B, and UV-Csubclassifications of such radiation.

The term “UV-A” means ultraviolet electromagnetic radiation with awavelength from about 320 nm to about 400 nm, and includes UV-A1 (fromabout 340 nm to about 400 nm) and UV-A2 (from about 320 nm to about 340nm).

The term “UV-B” means ultraviolet electromagnetic radiation with awavelength from about 290 nm to about 320 nm.

The term “UV-C” means ultraviolet electromagnetic radiation with awavelength from about 200 nm to about 290 nm.

The term “UV absorber” means compositions that absorb, reflect, and/orscatter UV radiation.

Personal care compositions refers to such illustrative non-limitingcompositions as skin, sun, oil, hair, cosmetic, and preservativecompositions, including those to alter the color and appearance of theskin. Other personal care compositions are those that enhanceflexibility in styling, durable styling, increased humidity resistancefor hair, skin, and color cosmetics, sun care water-proof/resistance,wear-resistance, and thermal protecting/enhancing compositions.

The term “sun-care formulation” means personal care and/orpharmaceutical formulations comprising an effective amount ofUV-absorbing compounds. Sun-care formulations include beach andnon-beach products that are applied to the face, décolleté, lips, andskin to treat and/or protect against erythema, burns, wrinkles, lentigo(“liver spots”), skin cancers, keratotic lesions, and cellular changesof the skin; and to hair to treat and/or protect against color changes,lack of luster, tangles, split ends, unmanageability, and embrittlement.

The term “performance chemicals application” refers to any applicationthat is not a personal care or pharmaceutical application. Examples ofperformance chemicals applications include, but are not limited to:adhesive, agricultural, cleaning, coating, construction material,encapsulation, ink, membrane, personal care, printing, plastic, orpackaging composition

All percentages, ratio, and proportions used herein are based on aweight basis unless other specified.

It has been discovered that performance-boosting UV absorber compoundsare provided by compounds derived from at least (a) a UV absorber havingat least one hydroxyl group, primary amine group, or secondary aminegroup, (b) a coupling agent having anhydride functionality, and (c) agraft host comprising an unsaturated fatty acid. Such compositions canbe produced via three pathways, the preferred being that the UV absorberis reacted with an ene graft reaction product between a molecule havinganhydride functionality and a graft host comprising an unsaturated fattyacid. The UV absorber compounds can be produced with or without addedreaction solvent, initiator, or catalyst, or blends thereof.

In preferred embodiments, coupling agent is maleic anhydride.

In addition to treating and/or protecting from the effects of radiationabsorption, these compositions do not suffer UV absorber loss byvolatilization, migration, or extraction, even at high temperatures,because the UV absorber is covalently bonded. As a direct consequence,the performance of products made with the invention's compositions areenhanced.

UV Absorber

The first required reactant is at least one UV absorber. Preferred UVabsorbers are those that exhibit UV-A activity or both UV-A and UV-Bactivity. Due to the wide array of potential UV-active chemistries, itis appreciated that a select number is suitable for human use, while amany of the other UV absorber chemistries find industrial use, e.g., inadhesives, coatings, encapsulations, inks, lacquers, packaging, paints,plastics, and varnishes. It is outside the scope of this invention tospecify all such actives in each application field, especially UVabsorbers approved for human use in different countries. Rather, thisinvention recognizes the specific reactive chemistries necessary toproduce the claimed compositions.

The UV absorbers of this invention exhibit at least one hydroxyl,primary amine, and/or secondary amine functionality. These specificfunctional groups are indicated as they open the ring structure of thegraft host.

Non-limiting examples of UV absorbers that exhibit the necessaryhydroxyl, primary amine, and/or secondary amine functionalities include:

p-aminobenzoic acid and its derivatives: 4-aminobenzoic acid (PABA);digalloyl triolate; 2,3-dihydroxypropyl 4-aminobenzoate (lisadimate,amyl dimethyl PABA, glyceryl PABA);ethyl-4-bis(hydroxypropyl)-aminobenzoate (roxadimate); ethoxylated ethyl4-aminobenzoate (PEG-25 PABA); hexyl2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (diethylamino hydroxybenzoyl hexylbenzoate); (5-methyl-2-propan-2-ylcyclohexyl)2-aminobenzoate (menthyl anthranilate, meradimate);

benzophenone derivatives:(2-hydroxy-4-methoxyphenyl)-(2-hydroxyphenyl)methanone (dioxybenzone,benzophenone-8); 2,2′,4,4′-tetrahydroxybenzophenone (benzophenone-2,Uvinul® D-50); 2-hydroxy-4-methoxybenzophenone (oxybenzone,benzophenone-3); 2,2′-dihydroxy-4,4′-dimethoxybenzophenone(benzophenone-6);2,2′-dihydroxy-4,4′-dimethoxybenzophenone-5,5′-disulphonic acid sodiumsalt (benzophenone-9);4-hydroxy-2-methoxy-5-(oxo-phenylmethyl)benzenesulfonic acid(sulisobenzone, benzophenone-4);2-hydroxy-4-methoxybenzophenone-5-sulphonic acid sodium salt(benzophenone-5), 2-aminobenzophenone;2-hydroxy-4-(octyloxy)phenyl)phenylmethanone;2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro(5.1.11.2)heneicosan-21-one,

benzotriazole derivatives:2-(benzotriazol-2-yl)-6-[[3-(benzotriazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]methyl]-4-(2,4,4-trimethylpentan-2-yl)phenol(bisoctrizole); 2-(2-hydroxy-5-methylphenyl)benzotriazole(drometrizole);2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-(1,3,3,3-tetramethyl-1-((trimethylsilyl)oxy)disiloxanyl)propyl)phenol(drometrizole trisiloxane):2,2′-methylenebis-[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol](methylenebis-benzotriazolyl tetramethylbutylphenol);2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (Uvinul®3029, Uvinul® 3029 GR);

benzimidazole derivatives: 2-phenylbenzimidazole-5-sulfonic acid and itspotassium, sodium and triethanolamine salts, (phenylbenzimidazolesulfonic acid, ensulizole);2,2′-(1,4-phenylene)bis-1Hbenzimidazole-4,6-disulfonic acid, monosodiumsalt (disodium phenyl dibenzimidazole tetrasulfonate);

camphor derivatives: α-(2-oxoborn-3-ylidene)-toluene-4-sulphonic acidand its salts (benzylidene camphor sulfonic acid);3,3′-(1,4-phenylenedimethylene)bis(7,7-dimethyl-2-oxobyciclo-[2.2.1]hept-1-ylmethanesulphonic acid and its salts (terephthalylidene dicamphor sulfonic acid,emcamsule); polymer of N-{(2 and4)-[(2-oxoborn-3-ylidene)methyl]benzyl}(polyacrylamido methylbenzylidenecamphor);

cinnamates: diethanolamine-p-methoxycinnamate (DEA methoxycinnamate);

quinones: lawsone with dihydroxyacetone;

salicylates: 2-ethylhexyl salicylate (ethylhexyl salicylate);3,3,5-trimethylcyclohexyl salicylate (homosalate, homomethylsalicylate); 2-(bis(2-hydroxyethyl)amino)ethyl 2-hydroxybenzoate(trolamine salicylate, triethanol amine salicylate);

triazine derivatives:2,4,6-trianilino-(p-carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine(ethylhexyl triazone);4,4′-[[6-[[[(1,1-dimethylethyl)amino]carbonyl]phenyl]amino]-1,3,5-triazine-2,4-diyl]diimino]bis-bis(2-ethylhexyl)benzoate(diethylhexyl butamido triazone, iscotrizinol);2,2′-[6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl]bis[5-[(2ethylhexyl)oxy]phenol(bis-ethylhexyloxyphenol methoxyphenyl triazine); and2,2′-[6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl]bis{5-[(2-ethylhexyl)oxy]phenol}(bemotrizinol, Tinosorb® S).

Examples of UV absorber having the necessary hydroxyl, primary amine, orsecondary amine functionalities include, without limitation:

amines: bis-benzoxazoyl phenyl ethylhexyl amino triazine;N,N′-bisformyl-N,N′-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylendiamine(Uvinul® 40450 H); bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate(Uvinul® 4077 H and 4077 GR); sterically hindered oligomeric amine, CASnumber 152261-33-1 (Uvinul® 5050H));N,N′-bisformyl-N,N′-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylendiamine(Uvinul® 4050H); N-(2-ethoxyphenyl)-N′-(2-ethylphenyl)oxamide

benzoates: methyl-2-aminobenzoate;

benzophenones: beta-2-glucopyranoxypropylhydroxybenzophenone;[2-hydroxy-4-(octyloxy)phenyl](phenyl)methanone (Uvinul® 3008 and 3008FL);

benzotriazoles:6-tert-butyl-2-(5-chloro-2H-benzotriazole-2-yl)-4-methylphenol (Uvinul®3026 and 3026 GR);2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazole-2-yl)-phenol (Uvinul®3027); 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol (Uvinul® 3028and 3028 GR); 2-(2H-benzotriazole-2-yl)-4-methylphenol (Uvinul® 3033 P);2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (Uvinul®3034);4-methylhexyl3-(3-benzotriazol-2-yl-4-hydroxy-5-tert-butyl-phenyl)propanoate;

cinnamates: (E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid (ferulicacid);

salicylates: 2-[bis(2-hydroxyethyl)amino]ethyl salicylate; and

triazones:2-[(p-(tert-butylamido)-anilino]-4,6-bis[(p-(2′-ethylhexyl-1′-oxycarbonyl)-anilino]-1,3,5-triazine.

The above mentioned UV absorbers at least one hydroxyl, primary amine,or secondary amine group generally contain 10 carbon atoms or more,preferably contain 20 carbon atoms or more.

Preferred embodiments of this invention that are UV-A actives include,but not limited to: 2-aminobenzophenone, bemotrizinol, bis-benzoxazoylphenyl ethylhexyl amino triazine, bisoctrizole,diethylaminohydroxybenzoylhexylbenzoate, diethylhexyl butamido triazone,dioxybenzone, disodium phenyl dibenzimidazole tetrasulfonate,drometrizole trisiloxane, ecamsule, ensulizole, menthyl anthranilate,meradimate, oxybenzone, sulisobenzone, and blends thereof.

Preferred embodiments of this invention that are UV-B actives include,but not limited to: aminobenzoic acid, amyl dimethyl PABA,benzophenone-9,3-benzylidene camphor sulfonic acid, bisoctrizole,camphor benzalkonium methosulfate, diethanolamine p-methoxycinnamate,diethylhexyl butamido triazone, digalloyl trioleate, drometrizoletrisiloxane, ensulizole, ethyl 4-bis(hydroxypropyl)aminobenzoate,ethylhexyl p-methoxycinnamate, 2-ethylhexyl salicylate, ethylhexyltriazone, glyceryl aminobenzoate, homomethyl salicylate, lawsone withdihydroxyacetone, meradimate, methoxycinnamido propyl hydroxy sultaine,oxybenzone (benzophenone-3), 2-phenylbenzimidazole-5-sulfonic acid (andits potassium, sodium and triethanolamine salts), sulisobenzone(benzophenone-4), and triethanolamine salicylate and bends thereof.

In especially preferred embodiments of this invention,performance-boosting UV absorber compounds comprise at least one UV-Aactive and at least one UV-B active. This is to say that at least oneUV-A active and at least one UV-B active are grafted onto the same ordifferent graft host compounds. Within the context of this embodiment,it is especially preferred that at least one UV-A active and at leastone UV-B active are grafted onto the same graft host compound to createa molecule with both UV-A and UV-B absorbing activity.

Anhydride Coupling Agent

In the present invention at least one anhydride coupling agent isprovided, which serves as a covalent bond agent between the UV absorberand the graft host that comprises an unsaturated fatty acid.

There are two forms that the anhydride coupling agent assumes. In oneform the anhydride coupling agent has a carbon-carbon double bond thatis able to graft to unsaturated fatty acid through an ene additionreaction. Non-limiting examples of this form of the anhydride couplingagent include: maleic anhydride, dimethyl maleic anhydride, itaconicanhydride, and citraconic anhydride, their derivatives, and blendsthereof.

Alternatively, the anhydride coupling agent is the abovedescribedanhydride coupling agent after the ene grafting reaction with the grafthost. In this form, the original carbon-carbon double bond is replacedwith a carbon-carbon single bond, and the anhydride coupling agent andthe graft host are one molecule. Non-limiting examples of this form ofthe anhydride coupling agent include: succinic anhydride and itsderivatives. Note that although the anhydride coupling agent in thisform may be “succinic anhydride,” it is common to refer to the enegrafted reaction product as “maleated,” e.g, “maleated oil”

In preferred embodiments, the anhydride coupling agent is maleicanhydride (first described form) and succinic anhydride adduct (seconddescribed form).

Graft Host Comprising an Unsaturated Fatty Acid

Another reactant to produce the UV absorber-absorbing compound is agraft host comprising an unsaturated fatty acid. Prior to the additionof the anhydride coupling agent, the graft host must comprise at leastone carbon-carbon double bond in order to enable the ene graftingreaction. As such, the graft host comprises an unsaturated fatty acid.However, after ene grafting reaction, it is possible to hydrogenate thereaction product to partially or completely saturate the alkenyl groups.

Unsaturated fatty acids are those compounds described by the structure:

wherein R₁ is hydrogen or the residue product from the esterification ofglycerol, and R₂ is an alkenyl chain. Fatty acids may be attached toother molecules, producing molecules known as “fats” and “oils,” andunattached to other molecules, in which case they are called, “freefatty acids.” Free fatty acids that exist in nature are termed, “naturalfatty acids.”

Natural fatty acids contain as few as 4 carbons (butyric acid) and asmany as 28 carbons (caprylic acid) or more. Many such naturalunsaturated fatty acids are known, and include: arachidonic acid,cervonic acid, clupanodinic acid, docosahexaenoic acid, eicosenoic acid,eicosapentaenoic acid, elaidic acid, erucic acid, gadoleic acid,hepatodecenoic acid, linoleic acid, conjugated linoleic acid,alpha-linoleic acid, gamma linolenic acid, dihomo-gamma-linoleic acid,myristoleic acid, oleic acid, palmitoleic acid, ricinoleic acid,timnodonic acid, vaccenic acid, and vernolic acid, and blends thereof.

As an alternative to free fatty acids, the graft host may take the formof a liquid-state oil, a soft-state butter, or a solid-state fat, orblends thereof. One common feature among these forms is that they areesterification product of three fatty acids with glycerol, which isknown by the generic name triglyceride and the following structure:

wherein R′, R″, and R′″ independently are alkyl or alkenyl groups, oneof which must be an alkenyl group. The state of matter for triglyceridesdepends on the nature of R′, R″, and R′″, and increasing fatty acidchain lengths enhances molecular entanglements, and thereby increasesthe melting point. Oils, butters, and fats find application in thisinvention provided they are exist in a liquid state during the reaction,e.g., solidified fats can be liquefied by heating them.

One non-limiting example of an unsaturated oil is soybean oil, which iscomposed of five major fatty acids: palmitate, stearate, oleate,linolenate, and linoleate. Hence, soybean oil may be represented by thefollowing molecule, which is derived from linolenate, and palmitatefatty acids:

Unsaturated butters and fats from animal and plant origin also areknown, and include, without limitation: cocoa butter, illipe butter,milk butter, shea butter, and mango butter and blends thereof. Likewise,unsaturated animal and plant fats are known, and include, withoutlimitation: beef fat, chicken fat, Japan wax, lards, mutton fat, pigfat, suets, and tallows.

Of course, many natural oils and fats are known.

Due to the inherent complexity of naturally-occurring materials, manyoils and fats contain a multiplicity of fatty acids and fat molecules.The only limitation in their suitability is that they comprise at least1 unsaturated carbon-carbon bond.

Additionally, natural and synthetic fats, such as triglycerides, can besynthesized in the laboratory in the reaction between free fatty acidsand glycerol

Synthesis of the Chromophore Composition

Three methods are provided for the production of the chromophorecompositions of this invention.

The first method is preferred, comprising the reaction of at least tworeactants: (a) the first of which is a UV absorber having at least onehydroxyl group, primary amine group, or secondary amine group, and (b)the second of which is a preformed ene grafting reaction product betweenan anhydride coupling agent and an unsaturated fatty acid. The reactivechromophore is grafted onto the anhydride moiety by ring opening of theanhydride.

A preferred compound comprising a maleated unsaturated fatty acid is amaleated vegetable oil, as described in U.S. Pat. No. 7,361,710.Maleated vegetable oils are favored in the current invention, as theydemonstrate low toxicity, sustainable production, and contribute toimproved persistence (water resistance) of the UV absorber compound.Maleated forms of unsaturated vegetable oils, include, but not limitedto: almond, castor, corn, cottonseed, linseed, mineral, olive, palmkernel, peanut, rapeseed, rice bran oil, sesame, soybean, sunflower, andtheir derivatives, and blends thereof.

The UV absorber compounds of this invention may be produced via a secondmethod, which comprises at least three reactants: (a) a chromophorecomprising hydroxyl group, primary amine group, and/or secondary aminegroup, (b) a coupling agent comprising anhydride functionality, and (c)a graft host comprising an unsaturated fatty acid. The UV absorberreacts with the coupling agent to open the anhydride ring. That reactionproduct is then grafted onto the compound comprising an unsaturatedfatty acid via an ene addition reaction.

Alternatively, the UV absorber compounds may be produced by a thirdmethod, which also comprises at least three reactants: (a) a UV absorberhaving at least one hydroxyl group, primary amine group, or secondaryamine group, (b) a coupling agent having anhydride functionality, and(c) a graft host comprising an unsaturated fatty acid. The couplingagent participates in an ene reaction with the graft host. Then, the UVabsorber opens the anhydride ring to yield the final UV absorberproduct.

It is within the scope of this invention to employ mixtures ofchromophores (e.g., UV-A and UV-B absorbers, UV and visible lightabsorbers). It may be advantageous to add the least reactive UVabsorbers first, and the more reactive ones later in the preparation.

Alternately, multiple UV absorbers can be blended together and used.Regardless of the type or number of UV absorbers, their total molarequivalents should not exceed the equivalents of the anhydride moiety inthe coupling agent. As necessary, additional reactive species can beattached to the composition. To properly adjust the stoichiometry ofmultiple reactive additives, the relative anhydride content must beconsidered.

The use of certain reactants and selection of reaction temperature mayresult in a reacting system of high viscosity, which may reduce thereaction yield. A resolution to this problem is the addition of anoptional reaction solvent. The reaction comprising the UV absorber andthe graft host may be carried out without or with added inert solvents,including: benzene, toluene, xylene, mesitylene, chlorobenzene,dimethylformamide, tetrahydrofuran, aliphatic hydrocarbons, and theCeraphyl® emollients product line of International Specialty Products(Wayne, N.J.), such as diisopropyl adipate (Ceraphyl® 230).

In some cases the reaction may stop at the intermediate amic acid form,or partial or complete conversion of the amic acid to the cyclic imideform may occur. Such conversion may occur if the reaction temperature issufficiently high, viz. above 225° C., or during an optional heattreatment, e.g., to reduce residual monomer concentration.Alternatively, catalyst may be added to the reaction to facilitate thisform conversion.

For example, a product of this invention, which comprises the UV-Babsorber 2-aminobenzoate, can be converted from its amic acid to imideform by heating, using a catalyst, or a combination of both:

The reaction may be carried out for times ranging from 30 seconds to 48hours or even more, depending upon (a) the degree of conversion to imideform that is desired, (b) the reactivity of the chromophores, (c) thereaction temperature employed, (d) the presence or absence of a solvent,and (e) the use or non-use of an initiator and/or catalyst. With the useof an optional reaction solvent or solvents, it may be preferred toremove the solvent(s) after the reaction, e.g., at reduced pressureand/or elevated temperature, and then to add a different solventconducive to the final formulation. Applying a vacuum may further helpto reduce the residual concentration(s) of the UV absorber(s).

Typically, the temperature ranges from 20° C. to the decompositiontemperature of any reactant. At lower reaction temperatures, UV absorberbearing primary and/or secondary amine group may become attached to theanhydride coupling agent as amic acid derivatives. Duringhigh-temperature processing, such and amic acid form will tend tocyclize to the imide form.

Since the UV absorber actives are covalently bonded to theanhydride-comprising graft host, they are not lost from the reactedproduct by volatilization, migration, or other mechanisms even at hightemperatures. As a result, the compositions of this invention areparticularly useful for extended product service life. Any unreacted(residual) UV absorber may be removed using methods known in the art.For example, when the UV absorber has a lower boiling point than thefinal product, the graft host or the ene-graft reacted graft host, thendistillation (e.g, vacuum distillation or thin film distillation) may beused.

The UV absorbing compounds of this invention are useful in personal careproducts, sun-care products, and in performance chemicals applications,including polymers and inks that otherwise degrade when exposed to solarradiation. Also contemplated is the use of the disclosed UV absorbingcompounds to protect wood, lignin, and foliage from UV damage.

The performance-boosting UV absorber compounds of this invention can beused together with other additives to further enhance the properties ofthe finished product. Examples of other additives that can be used inconjunction with the stabilizers of this invention include antioxidants,e.g., alkylated monophenols, alkylated hydroquinones, hydroxylatedthiodiphenyl ethers, alkylidene-bis-phenols, hindered phenolic benzylcompounds, acylaminophenols, esters of3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, esters of3-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid,3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amides; and otheradditives.

Optional: Initiator

An optional free radical initiator may be added to the reactants tograft the cited UN absorber onto the graft host. Advantages of using anoptional initiator(s) may include lower reaction temperatures and/ormore complete extent of reaction.

Compounds capable of initiating the free-radical polymerization includethose materials known to function in the prescribed manner, and includethe peroxo and azo classes of materials. Exemplary peroxo and azocompounds include, but are not limited to: acetyl peroxide; azobis-(2-amidinopropane)dihydrochloride; azo bis-isobutyronitrile;2,2′-azo bis-(2-methylbutyronitrile); benzoyl peroxide; di-tert-amylperoxide; di-tert-butyl diperphthalate; butyl peroctoate; tert-butyldicumyl peroxide; tert-butyl hydroperoxide; tert-butyl perbenzoate;tert-butyl permaleate; tert-butyl perisobutylrate; tert-butylperacetate; tert-butyl perpivalate; para-chlorobenzoyl peroxide; cumenehydroperoxide; diacetyl peroxide; dibenzoyl peroxide; dicumyl peroxide;didecanoyl peroxide; dilauroyl peroxide; diisopropyl peroxodicarbamate;dioctanoyl peroxide; lauroyl peroxide; octanoyl peroxide; succinylperoxide; and bis-(ortho-toluoyl) peroxide.

Also suitable to initiate the free-radical polymerization are initiatormixtures or redox initiator systems, including: ascorbic acid/iron(II)sulfate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodiumdisulfite, and tert-butyl hydroperoxide/sodium hydroxymethanesulfinate.

Optional: Additional Formulation Ingredients and Adjuvants

Optional additional formulation ingredients and adjuvants may beincorporated with the performance-boosting UV absorber compoundsdescribed herein. Such ingredients may be incorporated without alteringthe scope of the current invention, and may be included in order toproduce formulated products intended for end-use applications, includingthose for personal care and performance chemical applications such ascoatings, packaging, personal care, pharmaceutical items, plastics, andprinting.

The composition of the invention also can contain one or more additionalcosmetically acceptable additives chosen from conditioning agents,protecting agents, such as, for example, hydrosoluble, antiradicalagents, antioxidants, vitamins and pro-vitamins, fixing agents,oxidizing agents, reducing agents, dyes, cleansing agents, anionic,cationic, nonionic and amphoteric surfactants, thickeners, perfumes,pearlizing agents, stabilizers, pH adjusters, filters, preservatives,hydroxy acids, cationic and nonionic polyether associativepolyurethanes, polymers other than the cationic polymer describedherein, vegetable oils, mineral oils, synthetic oils, polyols such asglycols and glycerol, silicones, aliphatic alcohols, colorants,bleaching agents, highlighting agents and sequestrants. These additivesare present in the composition according to the invention in proportionsthat may range from 0 to 20% by weight in relation to the total weightof the composition. The precise amount of each additive may be easilydetermined by an expert in the field according to its nature and itsfunction.

Any known conditioning agent is useful in the personal care compositionsof this invention. Conditioning agents function to improve the cosmeticproperties of the hair, particularly softness, thickening, untangling,feel, and static electricity and may be in liquid, semi-solid, or solidform such as oils, waxes, or gums. Similarly, any known skin alteringagent is useful in the compositions of this invention. Preferredconditioning agents include cationic polymers, cationic surfactants andcationic silicones.

Conditioning agents may be chosen from synthesis oils, mineral oils,vegetable oils, fluorinated or perfluorinated oils, natural or syntheticwaxes, silicones, cationic polymers, proteins and hydrolyzed proteins,ceramide type compounds, cationic surfactants, fatty amines, fatty acidsand their derivatives, as well as mixtures of these different compounds.

The synthesis oils include polyolefins, e.g., poly-α-olefins such aspolybutenes, polyisobutenes and polydecenes. The polyolefins can behydrogenated.

The mineral oils suitable for use in the compositions of the inventioninclude hexadecane and oil of paraffin.

A list of suitable animal and vegetable oils comprises sunflower, corn,soy, avocado, jojoba, squash, raisin seed, sesame seed, walnut oils,fish oils, glycerol tricaprocaprylate, Purcellin oil or liquid jojoba,and blends thereof.

Suitable natural or synthetic oils include eucalyptus, lavender,vetiver, litsea cubeba, lemon, sandalwood, rosemary, chamomile, savory,nutmeg, cinnamon, hyssop, caraway, orange, geranium, cade, and bergamot.

Suitable natural and synthetic waxes include carnauba wax, candelilawax, alfa wax, paraffin wax, ozokerite wax, vegetable waxes such asolive wax, rice wax, hydrogenated jojoba wax, absolute flower waxes suchas black currant flower wax, animal waxes such as bees wax, modifiedbees wax (cerabellina), marine waxes and polyolefin waxes such aspolyethylene wax, and blends thereof.

The cationic polymers that may be used as a conditioning agent accordingto the invention are those known to improve the cosmetic properties ofhair treated by detergent compositions. The expression “cationicpolymer” as used herein, indicates any polymer containing cationicgroups and/or ionizable groups in cationic groups. The cationic polymersused generally have a molecular weight the average number of which fallsbetween about 500 and 5,000,000 and preferably between 1000 and3,000,000.

The preferred cationic polymers are chosen from among those containingunits including primary, secondary, tertiary, and/or quaternary aminegroups that may either form part of the main polymer chain or a sidechain.

Useful cationic polymers include known polyamine, polyaminoamide, andquaternary polyammonium types of polymers, such as:

-   -   (1) homopolymers and copolymers derived from acrylic or        methacrylic esters or amides. The copolymers can contain one or        more units derived from acrylamides, methacrylamides, diacetone        acrylamides, acrylamides and methacrylamides, acrylic or        methacrylic acids or their esters, vinyllactams such as vinyl        pyrrolidone or vinyl caprolactam, and vinyl esters. Specific        examples include: copolymers of acrylamide and dimethyl amino        ethyl methacrylate quaternized with dimethyl sulfate or with an        alkyl halide; copolymers of acrylamide and methacryloyl oxyethyl        trimethyl ammonium chloride; the copolymer of acrylamide and        methacryloyl oxyethyl trimethyl ammonium methosulfate;        copolymers of vinyl pyrrolidone/dialkylaminoalkyl acrylate or        methacrylate, optionally quaternized, such as the products sold        under the name Gafquat® by International Specialty Products; the        dimethyl amino ethyl methacrylate/vinyl caprolactam/vinyl        pyrrolidone terpolymers, such as the product sold under the name        Gaffix® VC 713 by International Specialty Products; the vinyl        pyrrolidone/methacrylamidopropyl dimethylamine copolymer,        marketed under the name Styleze® CC 10 by International        Specialty Products; and the vinyl pyrrolidone/quaternized        dimethyl amino propyl methacrylamide copolymers such as the        product sold under the name Gafquat® HS 100 by International        Specialty Products (Wayne, N.J.).    -   (2) derivatives of cellulose ethers containing quaternary        ammonium groups, such as hydroxy ethyl cellulose quaternary        ammonium that has reacted with an epoxide substituted by a        trimethyl ammonium group.    -   (3) derivatives of cationic cellulose such as cellulose        copolymers or derivatives of cellulose grafted with a        hydrosoluble quaternary ammonium monomer, as described in U.S.        Pat. No. 4,131,576, such as the hydroxy alkyl cellulose, and the        hydroxymethyl-, hydroxyethyl- or hydroxypropyl-cellulose grafted        with a salt of methacryloyl ethyl trimethyl ammonium,        methacrylamidopropyl trimethyl ammonium, or dimethyl diallyl        ammonium.    -   (4) cationic polysaccharides such as described in U.S. Pat. Nos.        3,589,578 and 4,031,307, guar gums containing cationic trialkyl        ammonium groups and guar gums modified by a salt, e.g., chloride        of 2,3-epoxy propyl trimethyl ammonium.    -   (5) polymers composed of piperazinyl units and alkylene or        hydroxy alkylene divalent radicals with straight or branched        chains, possibly interrupted by atoms of oxygen, sulfur,        nitrogen, or by aromatic or heterocyclic cycles, as well as the        products of the oxidation and/or quaternization of such        polymers.    -   (6) water-soluble polyamino amides prepared by polycondensation        of an acid compound with a polyamine. These polyamino amides may        be reticulated.    -   (7) derivatives of polyamino amides resulting from the        condensation of polyalcoylene polyamines with polycarboxylic        acids followed by alcoylation by bi-functional agents.    -   (8) polymers obtained by reaction of a polyalkylene polyamine        containing two primary amine groups and at least one secondary        amine group with a dioxycarboxylic acid chosen from among        diglycolic acid and saturated dicarboxylic aliphatic acids        having 3 to 8 atoms of carbon. Such polymers are described in        U.S. Pat. Nos. 3,227,615 and 2,961,347.    -   (9) the cyclopolymers of alkyl dialyl amine or dialkyl diallyl        ammonium such as the homopolymer of dimethyl diallyl ammonium        chloride and copolymers of diallyl dimethyl ammonium chloride        and acrylamide.    -   (10) quaternary diammonium polymers such as hexadimethrine        chloride.    -   (11) quaternary polyammonium polymers, including, for example,        Mirapol® A 15, Mirapol® AD1, Mirapol® AZ1, and Mirapol® 175        products sold by Miranol.    -   (12) the quaternary polymers of vinyl pyrrolidone and vinyl        imidazole such as the products sold under the names Luviquat® FC        905, FC 550, and FC 370 by BASF Corp. (Ludwigshafen, Del.).    -   (13) quaternary polyamines.    -   (14) reticulated polymers known in the art.

Other cationic polymers that may be used within the context of theinvention are cationic proteins or hydrolyzed cationic proteins,polyalkyleneimines such as polyethyleneimines, polymers containing vinylpyridine or vinyl pyridinium units, condensates of polyamines andepichlorhydrins, quaternary polyurethanes, and derivatives of chitin.

Preferred cationic polymers are derivatives of quaternary celluloseethers, the homopolymers and copolymers of dimethyl diallyl ammoniumchloride, quaternary polymers of vinyl pyrrolidone and vinyl imidazole,and mixtures thereof.

The conditioning agent can be any silicone known by those skilled in theart to be useful as a conditioning agent. The silicones suitable for useaccording to the invention include polyorganosiloxanes that areinsoluble in the composition. The silicones may be present in the formof oils, waxes, resins, or gums. They may be volatile or non-volatile.The silicones can be selected from polyalkyl siloxanes, polyarylsiloxanes, polyalkyl aryl siloxanes, silicone gums and resins, andpolyorgano siloxanes modified by organofunctional groups, and mixturesthereof.

Suitable polyalkyl siloxanes include polydimethyl siloxanes withterminal trimethyl silyl groups or terminal dimethyl silanol groups(dimethiconol) and polyalkyl (C₁-C₂₀) siloxanes.

Suitable polyalkyl aryl siloxanes include polydimethyl methyl phenylsiloxanes and polydimethyl diphenyl siloxanes, linear or branched.

The silicone gums suitable for use herein include polydiorganosiloxanespreferably having a number-average molecular weight between 200,000 and1,000,000, used alone or mixed with a solvent. Examples includepolymethyl siloxane, polydimethyl siloxane/methyl vinyl siloxane gums,polydimethyl siloxane/diphenyl siloxane, polydimethyl siloxane/phenylmethyl siloxane and polydimethyl siloxane/diphenyl siloxane/methyl vinylsiloxane.

Suitable silicone resins include silicones with a dimethyl/trimethylsiloxane structure and resins of the trimethyl siloxysilicate type.

The organo-modified silicones suitable for use in the invention includesilicones such as those previously defined and containing one or moreorganofunctional groups attached by means of a hydrocarbon radical andgrafted siliconated polymers. Particularly preferred are aminofunctional silicones.

The silicones may be used in the form of emulsions, nano-emulsions, ormicro-emulsions.

The conditioning agent can be a protein or hydrolyzed cationic ornon-cationic protein. Examples of these compounds include hydrolyzedcollagens having triethyl ammonium groups, hydrolyzed collagens havingtrimethyl ammonium and trimethyl stearyl ammonium chloride groups,hydrolyzed animal proteins having trimethyl benzyl ammonium groups(benzyltrimonium hydrolyzed animal protein), hydrolyzed proteins havinggroups of quaternary ammonium on the polypeptide chain, including atleast one C₁-C₁₈ alkyl.

Hydrolyzed proteins include Croquat L, in which the quaternary ammoniumgroups include a C₁₂ alkyl group, Croquat M, in which the quaternaryammonium groups include C₁₀-C₁₈ alkyl groups, Croquat S in which thequaternary ammonium groups include a C₁₈ alkyl group and Crotein Q inwhich the quaternary ammonium groups include at least one C₁-C₁₈ alkylgroup. These products are sold by Croda.

The conditioning agent can comprise quaternized vegetable proteins suchas wheat, corn, or soy proteins such as cocodimonium hydrolyzed wheatprotein, laurdimonium hydrolyzed wheat protein and steardimoniumhydrolyzed wheat protein.

2-N-stearoyl amino-octadecane-1,3-diol, 2-N-behenoylamino-octadecane-1,3-diol,2-N-[2-hydroxy-palmitoyl]-amino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3,4-triol, N-stearoyl phytosphingosine, 2-N-palmitoylamino-hexadecane-1,3-diol, bis-(N-hydroxy ethyl N-cetyl) malonamide,N-(2-hydroxy ethyl)-N-(3-cetoxyl-2-hydroxy propyl) amide of cetylicacid, N-docosanoyl N-methyl-D-glucamine and mixtures of such compounds.

The conditioning agent can be a cationic surfactant such as a salt of aprimary, secondary, or tertiary fatty amine, optionallypolyoxyalkylenated, a quaternary ammonium salt, a derivative ofimadazoline, or an amine oxide. Suitable examples include mono-, di-, ortri-alkyl quaternary ammonium compounds with a counterion such as achloride, methosulfate, tosylate, etc. including, but not limited to,cetrimonium chloride, dicetyldimonium chloride, behentrimoniummethosulfate, and the like. The presence of a quaternary ammoniumcompound in conjunction with the polymer described above reduces staticand enhances combing of hair in the dry state. The polymer also enhancesthe deposition of the quaternary ammonium compound onto the hairsubstrate thus enhancing the conditioning effect of hair.

The conditioning agent can be any fatty amine known to be useful as aconditioning agent; e.g. dodecyl, cetyl or stearyl amines, such asstearamidopropyl dimethylamine.

The conditioning agent can be a fatty acid or derivatives thereof knownto be useful as conditioning agents. Suitable fatty acids includemyristic acid, palmitic acid, stearic acid, behenic acid, oleic acid,linoleic acid, and isostearic acid. The derivatives of fatty acidsinclude carboxylic ester acids including mono-, di-, tri- andtetra-carboxylic acids.

The conditioning agent can be a fluorinated or perfluorinated oil. Thefluoridated oils may also be fluorocarbons such as fluoramines, e.g.,perfluorotributylamine, fluoridated hydrocarbons, such asperfluorodecahydronaphthalene, fluoroesters, and fluoroethers.

Of course, mixtures of two or more conditioning agents can be used.

The conditioning agent or agents can be present in an amount of 0.001%to 20%, preferably from 0.01% to 10%, and even more preferably from 0.1%to 3% by weight based on the total weight of the final composition.

The composition of the invention can contain one or more protectingagents to prevent or limit the degrading effects of natural physicaland/or chemical assaults on the keratinous materials.

The antioxidants or antiradical agents can be selected from phenols suchas BHA (tert-butyl-4-hydroxy anisole), BHT (2,6-di-tert-butyl-p-cresol),TBHQ (tert-butyl hydroquinone), polyphenols such as proanthocyanodicoligomers, flavonoids, hindered amines such as tetra amino piperidine,erythorbic acid, polyamines such as spermine, cysteine, glutathione,superoxide dismutase, and lactoferrin.

The vitamins can be selected from ascorbic acid (vitamin C), vitamin E,vitamin E acetate, vitamin E phosphate, B vitamins such as B3 and B5,vitamin PP, vitamin A, and derivatives thereof. The provitamins can beselected from panthenol and retinol.

The protecting agent can be present in an amount 0.001% to 20% byweight, preferably from 0.01% to 10% by weight, and more preferably 0.1to 5% by weight of the total weight of the final composition.

In addition, the compositions according to the invention advantageouslyinclude at least one surfactant, which can be present in an amount of0.1% and 60% preferably 1% and 40%, and more preferably 5% and 30% byweight based on the total weight of the composition. The surfactant maybe chosen from among anionic, amphoteric, or non-ionic surfactants, ormixtures of them known to be useful in personal care compositions.

Additional thickeners or viscosity increasing agents may be included inthe composition of the invention, such as: Acetamide MEA;acrylamide/ethalkonium chloride acrylate copolymer;acrylamide/ethyltrimonium chloride acrylate/ethalkonium chlorideacrylate copolymer; acrylamides copolymer; acrylamide/sodium acrylatecopolymer; acrylamide/sodium acryloyldimethyltaurate copolymer;acrylates/acetoacetoxyethyl methacrylate copolymer;acrylates/beheneth-25 methacrylate copolymer; acrylates/C₁₀-C₃₀ alkylacrylate crosspolymer; acrylates/ceteth-20 itaconate copolymer;acrylates/ceteth-20 methacrylate copolymer; acrylates/laureth-25methacrylate copolymer; acrylates/palmeth-25 acrylate copolymer;acrylates/palmeth-25 itaconate copolymer; acrylates/steareth-50 acrylatecopolymer; acrylates/steareth-20 itaconate copolymer;acrylates/steareth-20 methacrylate copolymer; acrylates/stearylmethacrylate copolymer; acrylates/vinyl isodecanoate crosspolymer;acrylic acid/acrylonitrogens copolymer; adipic acid/methyl DEAcrosspolymer; agar; agarose; alcaligenes polysaccharides; algin; alginicacid; almondamide DEA; almondamidopropyl betaine; aluminum/magnesiumhydroxide stearate; ammonium acrylates/acrylonitrogens copolymer;ammonium acrylates copolymer; ammonium acryloyldimethyltaurate/vinylformamide copolymer; ammonium acryloyldimethyltaurate/VP copolymer;ammonium alginate; ammonium chloride; ammonium polyacryloyldimethyltaurate; ammonium sulfate; amylopectin; apricotamide DEA;apricotamidopropyl betaine; arachidyl alcohol; arachidyl glycol; arachishypogaea (peanut) flour; ascorbyl methylsilanol pectinate; astragalusgummifer gum; attapulgite; avena sativa (oat) kernel flour; avocadamideDEA; avocadamidopropyl betaine; azelamide MEA; babassuamide DEA;babassuamide MEA; babassuamidopropyl betaine; behenamide DEA; behenamideMEA; behenamidopropyl betaine; behenyl betaine; bentonite; butoxychitosan; caesalpinia spinosa gum; calcium alginate; calciumcarboxymethyl cellulose; calcium carrageenan; calcium chloride; calciumpotassium carbomer; calcium starch octenylsuccinate; C20-40 alkylstearate; canolamidopropyl betaine; capramide DEA;capryl/capramidopropyl betaine; carbomer; carboxybutyl chitosan;carboxymethyl cellulose acetate butyrate; carboxymethyl chitin;carboxymethyl chitosan; carboxymethyl dextran; carboxymethylhydroxyethylcellulose; carboxymethyl hydroxypropyl guar; carnitine;cellulose acetate propionate carboxylate; cellulose gum; ceratoniasiliqua gum; cetearyl alcohol; cetyl alcohol; cetyl babassuate; cetylbetaine; cetyl glycol; cetyl hydroxyethylcellulose; chimyl alcohol;cholesterol/HDI/pullulan copolymer; cholesteryl hexyl dicarbamatepullulan; citrus aurantium dulcis (orange) peel extract; cocamide DEA;cocamide MEA; cocamide MIPA; cocamidoethyl betaine; cocamidopropylbetaine; cocamidopropyl hydroxysultaine; coco-betaine;coco-hydroxysultaine; coconut alcohol; coco/oleamidopropyl betaine;coco-Sultaine; cocoyl sarcosinamide DEA; cornamide/cocamide DEA;cornamide DEA; croscarmellose; crosslinked bacillus/glucose/sodiumglutamate ferment; cyamopsis tetragonoloba (guar) gum; decyl alcohol;decyl betaine; dehydroxanthan gum; dextrin; dibenzylidene sorbitol;diethanolaminooleamide DEA; diglycol/CHDM/isophthalates/SIP copolymer;dihydroabietyl behenate; dihydrogenated tallow benzylmonium hectorite;dihydroxyaluminum aminoacetate; dimethicone/PEG-10 crosspolymer;dimethicone/PEG-15 crosspolymer; dimethicone propyl PG-betaine;dimethylacrylamide/acrylic acid/polystyrene ethyl methacrylatecopolymer; dimethylacrylamide/sodium acryloyldimethyltauratecrosspolymer; disteareth-100 IPDI; DMAPA acrylates/acrylicacid/acrylonitrogens copolymer; erucamidopropyl hydroxysultaine;ethylene/sodium acrylate copolymer; gelatin; gellan gum; glycerylalginate; glycine soja (soybean) flour; guar hydroxypropyltrimoniumchloride; hectorite; hyaluronic acid; hydrated silica; hydrogenatedpotato starch; hydrogenated tallow; hydrogenated tallowamide DEA;hydrogenated tallow betaine; hydroxybutyl methylcellulose; hydroxyethylacrylate/sodium acryloyldimethyl taurate copolymer;hydroxyethylcellulose; hydroxyethyl chitosan; hydroxyethylethylcellulose; hydroxyethyl stearamide-MIPA;hydroxylauryl/hydroxymyristyl betaine; hydroxypropylcellulose;hydroxypropyl chitosan; hydroxypropyl ethylenediamine carbomer;hydroxypropyl guar; hydroxypropyl methylcellulose; hydroxypropylmethylcellulose stearoxy ether; hydroxypropyl starch; hydroxypropylstarch phosphate; hydroxypropyl xanthan gum; hydroxystearamide MEA;isobutylene/sodium maleate copolymer; isostearamide DEA; isostearamideMEA; isostearamide mIPA; isostearamidopropyl betaine; lactamide MEA;lanolinamide DEA; lauramide DEA; lauramide MEA; lauramide MIPA;lauramide/myristamide DEA; lauramidopropyl betaine; lauramidopropylhydroxysultaine; laurimino bispropanediol; lauryl alcohol; laurylbetaine; lauryl hydroxysultaine; lauryl/myristyl glycol hydroxypropylether; lauryl sultaine; lecithinamide DEA; linoleamide DEA; linoleamideMEA; linoleamide MIPA; lithium magnesium silicate; lithium magnesiumsodium silicate; macrocystis pyrifera (kelp); magnesium alginate;magnesium/aluminum/hydroxide/carbonate; magnesium aluminum silicate;magnesium silicate; magnesium trisilicate; methoxy PEG-22/dodecyl glycolcopolymer; methylcellulose; methyl ethylcellulose; methylhydroxyethylcellulose; microcrystalline cellulose; milkamidopropylbetaine; minkamide DEA; minkamidopropyl betaine; MIPA-myristate;montmorillonite; Moroccan lava clay; myristamide DEA; myristamide MEA;myristamide MIPA; myristamidopropyl betaine; myristamidopropylhydroxysultaine; myristyl alcohol; myristyl betaine; natto gum;nonoxynyl hydroxyethylcellulose; oatamide MEA; oatamidopropyl betaine;octacosanyl glycol isostearate; octadecene/MA copolymer; oleamide DEA;oleamide MEA; oleamide MIPA; oleamidopropyl betaine; oleamidopropylhydroxysultaine; oleyl betaine; olivamide DEA; olivamidopropyl betaine;oliveamide MEA; palmamide DEA; palmamide MEA; palmamide MIPA;palmamidopropyl betaine; palmitamide DEA; palmitamide MEA;palmitamidopropyl betaine; palm kernel alcohol; palm kernelamide DEA;palm kernelamide MEA; palm kernelamide MIPA; palm kernelamidopropylbetaine; peanutamide MEA; peanutamide MIPA; pectin; PEG-800;PEG-crosspolymer; PEG-150/decyl alcohol/SMDI copolymer; PEG-175diisostearate; PEG-190 distearate; PEG-15 glyceryl tristearate; PEG-140glyceryl tristearate; PEG-240/HDI copolymer bis-decyltetradeceth-20ether; PEG-100/IPDI copolymer; PEG-180/laureth-50/TMMG copolymer;PEG-10/lauryl dimethicone crosspolymer; PEG-15/lauryl dimethiconecrosspolymer; PEG-2M; PEG-5M; PEG-7M; PEG-9M; PEG-14M; PEG-20M; PEG-23M;PEG-25M; PEG-45M; PEG-65M; PEG-90M; PEG-115M; PEG-160M; PEG-180M;PEG-120 methyl glucose trioleate; PEG-180/octoxynol-40/TMMG copolymer;PEG-150 pentaerythrityl tetrastearate; PEG-4 rapeseedamide;PEG-150/stearyl alcohol/SMDI copolymer; phaseolus angularis seed powder;polianthes tuberosa extract; polyacrylate-3; polyacrylic acid;polycyclopentadiene; polyether-1; polyethylene/isopropyl maleate/MAcopolyol; polyglyceryl-3 disiloxane dimethicone; polyglyceryl-3polydimethylsiloxyethyl dimethicone; polymethacrylic acid;polyquaternium-52; polyvinyl alcohol; potassium alginate; potassiumaluminum polyacrylate; potassium carbomer; potassium carrageenan;potassium chloride; potassium palmate; potassium polyacrylate; potassiumsulfate; potato starch modified; PPG-2 cocamide; PPG-1 hydroxyethylcaprylamide; PPG-2 hydroxyethyl cocamide; PPG-2 hydroxyethylcoco/isostearamide; PPG-3 hydroxyethyl soyamide; PPG-14 laureth-60 hexyldicarbamate; PPG-14 laureth-60 isophoryl dicarbamate; PPG-14 palmeth-60hexyl dicarbamate; propylene glycol alginate; PVP/decene copolymer; PVPmontmorillonite; pyrus cydonia seed; pyrus malus (apple) fiber;rhizobian gum; ricebranamide DEA; ricinoleamide DEA; ricinoleamide MEA;ricinoleamide MIPA; ricinoleamidopropyl betaine; ricinoleic acid/adipicacid/AEEA copolymer; rosa multiflora flower wax; sclerotium gum;sesamide DEA; sesamidopropyl betaine; sodium acrylate/acryloyldimethyltaurate copolymer; sodium acrylates/acrolein copolymer; sodiumacrylates/acrylonitrogens copolymer; sodium acrylates copolymer; sodiumacrylates crosspolymer; sodium acrylate/sodium acrylamidomethylpropanesulfonate copolymer; sodium acrylates/vinyl isodecanoate crosspolymer;sodium acrylate/vinyl alcohol copolymer; sodium carbomer; sodiumcarboxymethyl chitin; sodium carboxymethyl dextran; sodium carboxymethylbeta-glucan; sodium carboxymethyl starch; sodium carrageenan; sodiumcellulose sulfate; sodium chloride; sodium cyclodextrin sulfate; sodiumhydroxypropyl starch phosphate; sodium isooctylene/MA copolymer; sodiummagnesium fluorosilicate; sodium oleate; sodium palmitate; sodium palmkernelate; sodium polyacrylate; sodium polyacrylate starch; sodiumpolyacryloyldimethyl taurate; sodium polygamma-glutamate; sodiumpolymethacrylate; sodium polystyrene sulfonate; sodium silicoaluminate;sodium starch octenylsuccinate; sodium stearate; sodium stearoxyPG-hydroxyethylcellulose sulfonate; sodium styrene/acrylates copolymer;sodium sulfate; sodium tallowate; sodium tauride acrylates/acrylicacid/acrylonitrogens copolymer; sodium tocopheryl phosphate; solanumtuberosum (potato) starch; soyamide DEA; soyamidopropyl betaine;starch/acrylates/acrylamide copolymer; starch hydroxypropyltrimoniumchloride; stearamide AMP; stearamide DEA; stearamide DEA-distearate;stearamide DIBA-stearate; stearamide MEA; stearamide MEA-stearate;stearamide MIPA; stearamidopropyl betaine; steareth-60 cetyl ether;steareth-100/PEG-136/HDI copolymer; stearyl alcohol; stearyl betaine;sterculia urens gum; synthetic fluorphlogopite; tallamide DEA; tallowalcohol; tallowamide DEA; tallowamide MEA; tallowamidopropyl betaine;tallowamidopropyl hydroxysultaine; tallowamine oxide; tallow betaine;tallow dihydroxyethyl betaine; tamarindus indica seed gum; tapiocastarch; TEA-alginate; TEA-carbomer; TEA-hydrochloride; trideceth-2carboxamide MEA; tridecyl alcohol; triethylene glycol dibenzoate;trimethyl pentanol hydroxyethyl ether; triticum vulgare (wheat) germpowder; triticum vulgare (wheat) kernel flour; triticum vulgare (wheat)starch; tromethamine acrylates/acrylonitrogens copolymer; tromethaminemagnesium aluminum silicate; undecyl alcohol; undecylenamide DEA;undecylenamide MEA; undecylenamidopropyl betaine; welan gum; wheatgermamide DEA; wheat germamidopropyl betaine; xanthan gum; yeastbeta-glucan; yeast polysaccharides and zea mays (corn) starch.

Preferred thickeners or viscosity increasing agents include carbomer,aculyn and Stabileze®, e.g. crosslinked acrylic acid, crosslinkedpoly(methylvinyl ether/maleic anhydride) copolymer, acrylamides,carboxymethyl cellulose and the like.

The compositions according to the invention may be used to wash andtreat keratinous material such as hair, skin, eyelashes, eyebrows,fingernails, lips, and hairy skin.

The compositions according to the invention may also take the form ofafter-shampoo compositions, to be rinsed off or not, for permanents,straightening, waving, dyeing, or bleaching, or the form of rinsecompositions to be applied before or after dyeing, bleaching,permanents, straightening, relaxing, waving or even between the twostages of a permanent or straightening process.

The compositions of the invention may also take the form of skin-washingcompositions, and particularly in the form of solutions or gels for thebath or shower, or of make-up removal products.

The compositions of the invention may also be in the form of aqueous orhydro-alcoholic solutions for skin and/or hair care.

The compositions according to the invention can be detergentcompositions such as shampoos, bath gels, and bubble baths. In thismode, the compositions will comprise a generally aqueous washing base.The surfactant or surfactants that form the washing base may be chosenalone or in blends, from known anionic, amphoteric, or non-ionicsurfactants. The quantity and quality of the washing base must besufficient to impart a satisfactory foaming and/or detergent value tothe final composition. The washing base can be from 4% to 50% by weight,preferably from 6% to 35% by weight, and even more preferentially from8% to 25% by weight of the total weight of the final composition.

With respect to personal care products, additional formulationingredients of particular interest are those selected from the listcomprising: anti-oxidants, bronzing/self-tanning agents, colorants,defoamers, emollients, fragrances, humectants, insect repellants, lowermonoalcohols, lower polyols, micro- and nano-particulate UV absorbants,moisturizers, pigments, preservatives, propellants, oils, surfactants,thickeners, water, and waxes.

With respect to coatings, packaging, plastics, and/or printing product,additional formulation ingredients of particular interest are selectedfrom the list comprising: colorants, defoamers, dyes, fragrances,lacquers, lakes, latexes, micro- and nano-particulate UV absorbents,pigments, plasticizers, preservatives (including biocides), solvents,surfactants, thickeners, varnishes, and water.

Product Forms

The UV absorbing compounds of this invention find use in a large numberof product forms. In one embodiment, the UV absorber takes the form of afilm, e.g., applied neat or from a solvent-evaporation step. Inpreferred embodiments, the UV absorbing compounds are employed inpersonal care, sun-care, or performance chemicals formulations.

Personal care compositions according to the invention may, for example,be used as care and/or sun protection product for the face and/or thebody having a consistency ranging from liquid to semiliquid (e.g.,milks, creams), and gels, creams, pastes, powders (including compactedpowders), and wax-like compositions.

For compositions intended to protect the hair from UV radiation,suitable product forms include, but not limited to: conditioners,dispersions, emulsions, gels, lotions, mists, mousses, shampoos, andsprays.

Optionally, formulations comprising the UV absorber compound may bepackaged as an aerosol and may be provided in the form of a mousse or aspray. It may be advantageous to utilize known propellants (e.g.,hydrofluorinated compounds dichlorodifluoromethane, difluoroethane,dimethyl ether, isobutene, N-butane, propane, trichlorofluoromethane) toaide in their delivery.

In a different embodiment, compositions of this invention may beprovided in the form of vaporizable fluid lotions to be applied to theskin or the hair. Pressurized devices are a suitable means forvaporizing fluid lotions, and are known to one skilled in the art. Forexample, they are described in U.S. Pat. Nos. 4,077,441 and 4,850,517.

The UV absorbing compounds may be formulated for performance chemicalapplications, e.g., be provided in a form suitable for brush or rollercoating of wood surfaces and substrates, or provided in an atomizableform for spraying plants, trees, and crops. Selection of the graft hostcomprising an unsaturated fatty acid can influence the properties of thefinal formulation, for example, viscosity and penetrationcharacteristics

Formulating the compounds of the invention as a stable microemulsion inwater may be accomplished using the method taught in US patentapplication 2008/0081059, the entire contents of which are herebyincorporated by reference.

Due to the great potential for controlling the anhydride and UV absorberaddition levels, the product may comprise from 0.01% to 100% of thedescribed UV absorber compound

Characterizing of the Product

The characterization of the UV absorber compound can be analyzed byknown techniques. Especially preferred are the techniques of ¹³C nuclearmagnetic resonance (NMR) spectroscopy, gas chromatography (GC), and gelpermeation chromatography (GPC) in order to decipher polymer identity,residual UV-A and UV-B concentrations, and polymer molecular weight andpolymer molecular weight distribution.

Nuclear magnetic resonance (NMR) spectroscopy is an especially preferredmethod to probe the polymerization product in terms of chemicalproperties such as monomeric composition, sequencing and tacticity.Analytical equipment suitable for these analyses include the Inova400-MR NMR System by Varian Inc. (Palo Alto, Calif.). References broadlydescribing NMR include: Yoder, C. H. and Schaeffer Jr., C. D.,Introduction to Multinuclear NMR, The Benjamin/Cummings PublishingCompany, Inc., 1987; and Silverstein, R. M., et al., SpectrometricIdentification of Organic Compounds, John Wiley & Sons, 1981, which areincorporated in their entirety by reference.

Residual monomer levels can be measured by GC, which can be used toindicate the extent of reactant conversion by the polymerizationprocess. GC analytical equipment to perform these tests are commerciallyavailable, and include the following units: Series 5880, 5890, and 6890GC-FID and GC-TCD by Agilent Technologies, Inc. (Santa Clara, Calif.).GC principles are described in Modern Practice of Gas Chromatography,third edition (John Wiley & Sons, 1995) by Robert L. Grob and Eugene F.Barry, which is hereby incorporated in its entirety by reference.

GPC is an analytical method that separates molecules based on theirhydrodynamic volume (or size) in solution of the mobile phase, such ashydroalcoholic solutions with surfactants. GPC is a preferred method formeasuring polymer molecular weight distributions. This technique can beperformed on known analytical equipment sold for this purpose, andinclude the TDAmax™ Elevated Temperature GPC System and the RImax™Conventional Calibration System by Viscotek™ Corp. (Houston, Tex.). Inaddition, GPC employs analytical standards as a reference, of which aplurality of narrow-distribution polyethylene glycol and polyethyleneoxide standards representing a wide range in molecular weight is thepreferred. These analytical standards are available for purchase fromRohm & Haas Company (Philadelphia, Pa.) and Varian Inc. (Palo Alto,Calif.). GPC is described in the following texts, which are herebyincorporated in their entirety by reference: Schroder, E., et al.,Polymer Characterization, Hanser Publishers, 1989; Billingham, N.C.,Molar Mass Measurements in Polymer Science, Halsted Press, 1979; andBillmeyer, F., Textbook of Polymer Science, Wiley Interscience, 1984.

The invention will now be described with reference to the followingexamples:

EXAMPLES Maleination Reaction 1: Grafting Maleic Anhydride onto SoybeanOil without Initiator

R″ and R″ are alkyl and alkenyl groups that are naturally occur insoybean oil.

Into a 1-L, 4-necked kettle equipped with a thermocouple, a condenser, anitrogen purge adaptor, and a mechanical stirrer, 391 g soybean oil and109 g of maleic anhydride were charged. The mixture temperature wasslowly raised over 30 minutes from room temperature (about 22° C.) to210° C., and then held isothermally for about 5-6 hours. Completion ofthe reaction was indicated when a drop of the reacting solution did nottriphenylphosphine test paper orange-red in color.

Example 1: Grafting a UV-B Absorber onto Maleated Soybean Oil (withoutInitiator)

R″ and R′″ comprise fatty acids that naturally occur in soybean oil.

In a 1-L, 4-necked kettle equipped with a thermocouple, a condenser, anitrogen purge adaptor, and a mechanical stirrer, 100 g of MaleinationReaction 1 product and 30 g of methyl-2-aminobenzoate, a UV-B absorber,were mixed and heated to 80° C. and held for 21 hours.

Maleination Reaction 2: Grafting Maleic Anhydride onto Soybean Oil withInitiator

In a 1-L, 4-necked kettle equipped with a thermocouple, a condenser, anitrogen purge adaptor, and a mechanical stirrer, 400 g soybean oil werecharged. The mixture was heated to 130° C. under nitrogen purge, andheld isothermally for 30 minutes. Then, 6.0 g of di-tert-butyl peroxide(DTPO) were charged, and then 6.67 g of maleic anhydride were chargedevery 10 minutes over the course of 1 hour (total amount of maleicanhydride charged: 40 g). Thirty minutes later, another 6.0 g of DTPOwere charged to the vessel. The reactor was held isothermally at 130° C.for about 5-6 hours. Completion of the reaction was indicated when adrop of the reacting solution failed to turn triphenylphosphine testpaper orange-red.

Example 2: Grafting a UV-B Absorber onto Maleated Soybean Oil (withInitiator)

In a 1-L, 4-necked kettle equipped with a thermocouple, a condenser, anitrogen purge adaptor, and a mechanical stirrer, 200 g of MaleinationReaction 2 product and 30 g of methyl-2-aminobenzoate, a UV-B absorber,were mixed and heated to 80° C. and held for 19 hours.

Example 3: Grafting a UV-A Absorber onto Maleated Soybean Oil (withInitiator)

R″ and R′″ comprise fatty acids that naturally occur in soybean oil.

In a 1-L, 4-necked kettle equipped with a thermocouple, a condenser, anitrogen purge adaptor, and a mechanical stirrer, 200 g of MaleinationReaction 2 product and 36 g of 2-aminobenzophenone, a UV-A absorber,were mixed and heated to 130° C. and held for 40 hours.

Example 4: Grafting UV-A and UV-B Absorbers onto Maleated Soybean Oil(with Initiator)

R″ and R′″ are alkyl or alkenyl groups that naturally occur in soybeanoil.

In a 1-L, 4-necked kettle equipped with a thermocouple, a condenser, anitrogen purge adaptor, and a mechanical stirrer, 200 g of MaleinationReaction 2 product, 26.9 g of 2-aminobenzophenone (a UV-A absorber), and20.6 g of methyl 2-aminobenzoate (a UV-B absorber) were mixed and heatedto 130° C. and held for 48 hours.

Example 5: Grafting UV-A and UV-B Absorbers onto Maleated Soybean Oil(with Initiator)

Example 4 was repeated, but after mixing the reactants they were heatedto 80° C. and held for 48 hours.

Example 6

Example 4 was repeated, but after mixing the reactants they were heatedto 170° C. and held for 72 hours.

Maleination Reaction 3: Grafting Maleic Anhydride onto Soybean Oilwithout Initiator

In a 1-L, 4-necked kettle equipped with a thermocouple, a condenser, anitrogen purge adaptor, and a mechanical stirrer, 200 g soybean oil werecharged. The mixture was slowly heated for 30 minutes from roomtemperature (about 22° C.) to 210° C. Then, 60 g of maleic anhydridewere charged and the mixture was held isothermally at 210° C. After 1.5hours, another 60 g charge of maleic anhydride was fed to the reactor,and the reactor was held isothermally at 210° C. for about 5-6 hours.Completion of the reaction was indicated when a drop of the reactingsolution did not turn triphenylphosphine test paper orange-red.

Example 7: Grafting UV-B Absorber onto Maleated Soybean Oil (withInitiator)

In a 1-L, 4-necked kettle equipped with a thermocouple, a condenser, anitrogen purge adaptor, and a mechanical stirrer, 100 g of product fromMaleination Reaction 3 and 56.6 g of methyl 2-aminobenzoate were mixedand heated to 130° C. and held for 54 hours.

Example 8: Grafting UV-A Absorber onto Maleated Soybean Oil (withInitiator)

In a 1-L, 4-necked kettle equipped with a thermocouple, a condenser, anitrogen purge adaptor, and a mechanical stirrer, 50 g of product fromMaleination Reaction 3 and 68 g of 2-aminobenzophenone were mixed andheated to 130° C. and held for 42 hours.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

What is claimed is:
 1. A method of preparing a UV-absorbing compoundthat comprises the steps: (a) selecting a UV absorber having at leastone hydroxyl group, primary amine, or secondary amine group, and furthercomprising one or more of a ρ-aminobenzoic derivative, benzophenonederivative, benzotriazole derivative, benzimidazole derivative, camphorderivative, cinnamate, quinone, salicylate, or triazine derivative, (b)selecting a preformed ene graft reaction product formed from an enegraft reaction between an anhydride coupling agent and an unsaturatedfatty acid, (c) creating a mixture comprising the components of steps(a) and (b), and (d) heating said mixture to a temperature from about50° C. to about 250° C.
 2. The method of claim 1 additionally comprisesthe steps of (a) selecting at least one initiator, reaction solvent, orcatalyst, and (b) adding to said mixture.
 3. A method of preparing aUV-absorbing compound that comprises the steps: (a) selecting a UVabsorber having at least one hydroxyl group, primary amine, or secondaryamine group, and further comprising one or more of a ρ-aminobenzoicderivative, benzophenone derivative, benzotriazole derivative,benzimidazole derivative, camphor derivative, cinnamate, quinone,salicylate, or triazine derivative, (b) selecting an anhydride couplingagent (c) selecting an unsaturated fatty acid, (d) creating a mixturecomprising the components of steps (a) through (c), and (e) heating saidmixtures to a temperature range from about 50° C. to about 250° C. 4.The method of claim 3 additionally comprising the steps of (a) selectingat least one initiator, reaction solvent, or catalyst, and (b) adding tosaid mixture.
 5. The method of claim 1 wherein the UV absorber isselected from the group consisting of: aminobenzoic acid;2-aminobenzophenone; amyl dimethyl PABA; bemotrizinol; benzophenone-3;benzophenone-4; benzophenone-9; 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol; 2-(2H-benzotriazole-2-yl)-4-methylphenol;2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol;bis-benzoxazoyl phenyl ethylhexyl amino triazine; 3-benzylidene camphorsulfonic acid;N,N-bisformyl-N,N-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylendi-amine;bisoctrizole; 2-Rp-(tert-butylamido)-anilino]-4,6,-bis[(p-(2′-ethylhexyl-1′-oxycarbony-1)-anilinol-1,3,5-triazine;6-tert-butyl-2-(5-chloro-2H-benzotriazole-2-yl)-4-methylphenol;2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazole-2-yl)-phenol; camphorbenzalkonium methosulfate; diethanolamine p-methoxycinnamate;diethylaminohydroxybenzoylhexylbenzoate; diethylhexyl butamido triazone;digalloyl trioleate; dioxybenzone; disodium phenyl dibenzimidazoletetrasulfonate; drometrizole trisiloxane; ecamsule; ensulizole; ethyl4-bis(hydroxypropyl)aminobenzoate; ethylhexyl p-methoxycinnamate;2-ethylhexyl salicylate; ethylhexyl triazone;beta-2-glucopyranoxypropylhydroxybenzophenone; glyceryl aminobenzoate;homomethyl salicylate; [2-hydroxy-4-(octyloxy)phenyl](phenyl)methanone;2-[bis (2-hydroxyethyl)amino] ethyl salicylate;(E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid; lawsone withdihydroxyacetone; meradimate; methoxycinnamido propyl hydroxy sultainementhyl anthranilate; meradimate; methyl-2-aminobenzoate; oxybenzone;2-phenylbenzimidazole-5-sulfonic acid (and its potassium, sodium andtriethanolamine salts); sulisobenzone;bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate; sterically hinderedoligomeric amine; triethanolamine salicylate;N-(2-ethoxyphenyl)-N-(2-ethylphenyl)oxamide; 4-methylhexyl3-(3-benzotriazol-2-yl-4-hydroxy-5-tert-butyl-phenyl) propanoate; andcombinations thereof.
 6. The method of claim 1 wherein selecting a UVabsorber further comprises selecting a first UV absorber and a second UVabsorber, each of the first and second UV absorber having at least onehydroxyl group, primary amine, or secondary amine group.
 7. The methodof claim 6 wherein the one of the first and second UV absorber is a UV-Aactive and the other of the first and second UV absorber is a UV-Bactive.
 8. The method of claim 1 further comprising hydrogenating thepreformed ene graft reaction product.
 9. The method of claim 3 whereinselecting a UV absorber further comprises selecting a first UV absorberand a second UV absorber, each of the first and second UV absorberhaving at least one hydroxyl group, primary amine, or secondary aminegroup.
 10. The method of claim 3 wherein the UV absorber is selectedfrom the group consisting of: aminobenzoic acid; 2-aminobenzophenone;amyl dimethyl PABA; bemotrizinol; benzophenone-3; benzophenone-4;benzophenone-9; 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol;2-(2H-benzotriazole-2-yl)-4-methylphenol;2-(2H-benzotriazole-2-yl)-4,6-bis (1-methyl-1-phenylethyl)phenol;bis-benzoxazoyl phenyl ethylhexyl amino triazine; 3-benzylidene camphorsulfonic acid;N,N-bisformyl-N,N-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylendi-amine;bisoctrizole; 2-Rp-(tert-butylamido)-anilino]-4,6,-bis[(p-(2′-ethylhexyl-1′-oxycarbony-1)-anilinol-1,3,5-triazine;6-tert-butyl-2-(5-chloro-2H-benzotriazole-2-yl)-4-methylphenol;2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazole-2-yl)-phenol; camphorbenzalkonium methosulfate; diethanolamine p-methoxycinnamate;diethylaminohydroxybenzoylhexylbenzoate; diethylhexyl butamido triazone;digalloyl trioleate; dioxybenzone; disodium phenyl dibenzimidazoletetrasulfonate; drometrizole trisiloxane; ecamsule; ensulizole; ethyl4-bis(hydroxypropyl)aminobenzoate; ethylhexyl p-methoxycinnamate;2-ethylhexyl salicylate; ethylhexyl triazone;beta-2-glucopyranoxypropylhydroxybenzophenone; glyceryl aminobenzoate;homomethyl salicylate; [2-hydroxy-4-(octyloxy)phenyl](phenyl)methanone;2-[bis (2-hydroxyethyl)amino] ethyl salicylate;(E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid; lawsone withdihydroxyacetone; meradimate; methoxycinnamido propyl hydroxy sultainementhyl anthranilate; meradimate; methyl-2-aminobenzoate; oxybenzone;2-phenylbenzimidazole-5-sulfonic acid (and its potassium, sodium andtriethanolamine salts); sulisobenzone;bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate; sterically hinderedoligomeric amine; triethanolamine salicylate;N-(2-ethoxyphenyl)-N-(2-ethylphenyl)oxamide; 4-methylhexyl3-(3-benzotriazol-2-yl-4-hydroxy-5-tert-butyl-phenyl) propanoate; andcombinations thereof.